Curable resin composition for use in water-based coating materials

Abstract

PCT No. PCT/JP96/03476 Sec. 371 Date Jul. 22, 1997 Sec. 102(e) Date Jul. 22, 1997 PCT Filed Nov. 28, 1996 PCT Pub. No. WO97/20004 PCT Pub. Date May 6, 1997The present invention relates to a curable resin composition for use in water-based coating materials which includes as essential components an emulsion polymer (A) containing tertiary amino groups obtained by carrying out emulsion polymerization of a vinyl monomer containing a tertiary amino group with another copolymerizable vinyl monomer in a water-based medium, and a compound (B) containing, at least, an epoxy group and a hydrolyzable silyl group, with this composition preferably also including a water-based compound (C) obtained by adding a neutralizing agent to a vinyl polymer (I) containing acidic groups and/or tertiary amino groups so as to neutralize at least 10% of the acidic groups and/or the tertiary amino groups, and then dispersing or dissolving in water, and/or a compound (D), which is not included in compound (B), and contains hydrolyzable silyl group and/or a silanol group. The coating material provided by the composition of the present invention is curable at ambient temperatures and demonstrates excellent coating properties. Moreover, the cured coating obtained from the composition of the present invention offers superior resistance to weathering, solvents, chemicals and water, and is not problematic with respect to conservation of the environment.

We claim: 
     
       1. A curable resin composition for use in water-based coating materials consisting essentially of, in combination,: an emulsion polymer (A), containing tertiary amino groups, obtained by carrying out emulsion polymerization of a vinyl monomer containing a tertiary amino group with another copolymerizable vinyl monomer in a water-based medium, and a compound (B) containing an epoxy group and a hydrolyzable silyl group,   wherein the emulsion polymer (A) is obtained by means of a soap-free polymerization method, and   the emulsion polymer (A) is neutralized with an acidic compound at some point in the soap-free polymerization so that the ratio of the equivalent weight of the acidic compound to that of amino groups in said emulsion polymer (A) containing tertiary amino groups is 0.1 or more.   
     
     
       2. A curable resin composition for use in water-based coating materials comprising, in combination,: an emulsion polymer (A), containing tertiary amino groups, obtained by carrying out emulsion polymerization of a vinyl monomer containing a tertiary amino group with another copolymerizable vinyl monomer in a water-based medium;   a water-based compound (C) obtained by adding a neutralizing agent to a vinyl polymer (I) containing acidic groups and/or tertiary amino groups so as to neutralize at least 10% of said acidic groups and/or said tertiary amino groups, and then dispersing or dissolving in water; and   a compound (B) containing an epoxy group and a hydrolyzable silyl group.   
     
     
       3. A curable resin composition for use in water-based coating materials comprising, in combination,: an emulsion polymer (A), containing tertiary amino groups, obtained by carrying out emulsion polymerization of a vinyl monomer containing a tertiary amino group with another copolymerizable vinyl monomer in a water-based medium;   a compound (B) containing an epoxy group and a hydrolyzable silyl group; and   a compound (D), different from and in addition to compound (B), containing a hydrolyzable silyl group and/or silanol group.   
     
     
       4. A curable resin composition for use in water-based coating materials comprising, in combination,: an emulsion polymer (A), containing tertiary amino groups, obtained by carrying out emulsion polymerization of a vinyl monomer containing a tertiary amino group with another copolymerizable vinyl monomer in a water-based medium;   a water-based compound (C) obtained by adding a neutralizing agent to a vinyl polymer (I) containing acidic groups and/or tertiary amino groups so as to neutralize at least 10% of said acidic groups and/or said tertiary amino groups, and then dispersing or dissolving in water;   a compound (B) containing an epoxy group and a hydrolyzable silyl group; and   a compound (D), different from and in addition to compound (B), contains a hydrolyzable silyl group and/or silanol group.   
     
     
       5. A curable resin composition for use in water-base coating materials consisting essentially of, in combination: an emulsion polymer (A), containing tertiary amino groups, obtained by carrying out emulsion polymerization of a vinyl monomer containing a tertiary amino group with another copolymerizable vinyl monomer in a water-based medium, and a compound (B) containing an epoxy group and a hydrolyzable silyl group,   wherein the emulsion polymer (A) is obtained by means of a soap-free polymerization method, and   the emulsion polymer (A) is neutralized with a basic compound at some point in the soap-free polymerization so that a ratio of an equivalent weight of the basic compound to that of acidic groups in said emulsion polymer (A) containing tertiary amino groups is 0.1 or more.   
     
     
       6. A curable resin composition for use in water-based coating materials according to one of claims 1 through 4 and 5, wherein the emulsion polymer (A) containing tertiary amino groups also contains carboxyl groups. 
     
     
       7. A curable resin composition for use in water-based coating materials according to one of claims 1 through 4 and 5, wherein the emulsion polymer (A) containing tertiary amino groups is prepared by employing at least a vinyl monomer containing a hydroxyl group as a monomer component thereof. 
     
     
       8. A curable resin composition for use in water-based coating materials according to one of claims 1 through 4 and 5, wherein the emulsion polymer (A) containing tertiary amino groups is prepared by employing at least a vinyl monomer containing a cycloalkyl group as a monomer component thereof. 
     
     
       9. A curable resin composition for use in water-based coating materials according to one of claims 1 through 4, wherein the emulsion polymer (A), containing tertiary amino groups, is obtained by means of a soap-free polymerization method using an effective amount of emulsifying agent whereby improved water resistance of the cured composition is achieved. 
     
     
       10. A curable resin composition for use in water-based coating materials according to one of claims 2 through 4, wherein an emulsion polymer (A) containing tertiary amino groups is neutralized with an acidic compound so that the ratio of the equivalent weight of the acidic compound to that of amino groups in said emulsion polymer (A) containing tertiary amino groups is 0.1 or more. 
     
     
       11. A curable resin composition for use in water-based coating materials according to one of claims 2 through 4, wherein the emulsion polymer ( A) containing tertiary amino groups is neutralized with a basic compound so that a ratio of an equivalent weight of the basic compound to that of acidic groups in said emulsion polymer (A) containing tertiary amino groups is 0.1 or more. 
     
     
       12. A curable resin composition for use in water-based coating materials according to one of claims 1 through 4 and 5, wherein an emulsion polymer (A) containing tertiary amino groups is an acrylic polymer. 
     
     
       13. A curable resin composition for use in water-based coating materials according to one of claims 2 or 4, wherein the vinyl polymer (I) containing acidic groups and/or tertiary amino groups is prepared using at least a vinyl monomer containing a hydroxyl group as a starting component. 
     
     
       14. A curable resin composition for use in water-based coating materials according to one of claims 2 or 4, wherein the vinyl polymer (I) containing acidic groups and/or tertiary amino groups is prepared using at least a vinyl monomer containing a cycloalkyl group as a starting component. 
     
     
       15. A curable resin composition for use in water-based coating materials according to one of claims 2 or 4, wherein the vinyl polymer (I), containing acidic groups and/or tertiary amino groups, comprises, in combination, an acrylic polymer and a fluoro olefin polymer. 
     
     
       16. A curable resin composition for use in water-based coating materials according to one of claims 2 or 4, wherein the vinyl polymer (I), containing acidic groups and/or tertiary amino groups, is a member selected from the group consisting of an acrylic polymer and a fluoro olefin polymer.